Storage node, phase change memory device and methods of operating and fabricating the same

ABSTRACT

A storage node, a phase change memory device, and methods of operating and fabricating the same are provided. The storage node may include a lower electrode, a phase change layer on the lower electrode and an upper electrode on the phase change layer, and the lower electrode and the upper electrode may be composed of thermoelectric materials having a melting point higher than that of the phase change layer, and having different conductivity types. An upper surface of the lower electrode may have a recessed shape, and a lower electrode contact layer may be provided between the lower electrode and the phase change layer. A thickness of the phase change layer may be about 100 nm or less, and the lower electrode may be composed of an n-type thermoelectric material, and the upper electrode may be composed of a p-type thermoelectric material, or they may be composed on the contrary to the above. Seeback coefficients of the lower electrode, the phase change layer, and the upper electrode may be different from each other.

PRIORITY STATEMENT

This application claims priority under 35 USC § 119 to Korean PatentApplication No. 10-2005-0102499, filed on Oct. 28, 2005, in the KoreanIntellectual Property Office (KIPO), the entire contents of which areincorporated herein by reference.

BACKGROUND

1. Field

Example embodiments relate to a storage node, a semiconductor memorydevice and methods of operating and fabricating the same. Other exampleembodiments relate to a storage node, a phase change memory device andmethods of operating and fabricating the same.

2. Description of the Related Art

A phase change random access memory (PRAM) may be one of non-volatilememory devices (e.g., a flash memory, a ferroelectric random accessmemory (FRAM) and/or a magnetic random access memory (MRAM)). Adifference of a PRAM and other non-volatile memory devices may be astructure of a storage node. The storage node of a PRAM may include aphase change layer. A phase of the phase change layer may be changedfrom a crystal state to an amorphous state at a predeterminedtemperature, and from an amorphous state to a crystal state at atemperature lower than the predetermined temperature.

If a resistance of a phase change layer when a phase of the phase changelayer is in an amorphous state is a first resistance, and a resistanceof the phase change layer when a phase of the phase change layer is in acrystal state is a second resistance, the first resistance may begreater than the second resistance. A PRAM may be a memory devicerecording and reading bit data, using resistance characteristics of aphase change layer that a resistance of the phase change layer may bevaried in accordance with a phase of the phase change layer as above.

FIG. 1 illustrates a conventional PRAM. Referring to FIG. 1, theconventional PRAM may include a transistor Tr, which may be composed ofa source region S and a drain region D, and a gate G formed on a channelregion C between the source and drain regions S and D, on a siliconsubstrate 7. The conventional PRAM may include a storage node 10connected to either one of the two regions S and D of the transistor Tr,for example, the source region S. The storage node 10 may be connectedto the source region S of the transistor Tr through a conductive plug 9.The storage node 10 may include a lower electrode 10 a, a lowerelectrode contact layer 10 b, a phase change layer 10 c in which bitdata may be recorded, and an upper electrode 10 d, which may besequentially stacked. The lower electrode 10 a may also function as apad layer providing a relatively wide area for the lower electrodecontact layer 10 b to be formed. The lower electrode contact layer 10 bmay contact a limited area below a bottom surface of the phase changelayer 10 c.

FIGS. 2(a)-2(c) illustrate a method of operating the conventional PRAM.In FIGS. 2(a)-2(c), the storage node 10 may be illustrated forconvenience. Referring to FIGS. 2(a)-2(c), it may be considered that theconventional PRAM is in a set state and that bit data 0 may be recordedwhen a phase of the phase change layer 10 c is in a crystal state. Afirst phase change current I1 may be applied from the upper electrode 10d through the phase change layer 10 c to the lower electrode 10 a in thestate that bit data 0 is recorded. The first phase change current I1 maybe a current changing a phase of the portion contacting the lowerelectrode contact layer 10 b of the phase change layer 10 c to anamorphous state, and may be called a reset current. The first phasechange current I1 may be a pulse current, and may be applied for severalnanoseconds, and may have a greater value than that of a set current.

The first phase change current I1 may be focused on the lower electrodecontact layer 10 b being narrower in width than the phase change layer10 c. As a resistance of a portion A1 (hereinafter, referred to as acontact area) of the phase change layer 10 c contacting the lowerelectrode contact layer 10 b is increased, a temperature of the contactarea A1 may increase up to a phase change temperature or higher whilethe first phase change current I1 is applied. A phase of the contactarea A1 of the phase change layer 10 c may be changed from a crystalstate to an amorphous state. As such, it may be considered that theconventional PRAM is in a reset state and that data 1 may be recordedwhen the contact area A1 of the phase change layer 10 c is in anamorphous state. A reference numeral h1 in FIG. 2(a) indicates a heightof the first phase change current I1.

As shown in FIG. 2(b), when the contact area A1 of the phase changelayer 10 c is in an amorphous state, a second phase change current 12may be applied to the storage node 10 in the same direction as that ofthe first phase change current I1. As the second phase change current I2changes the phase of the contact area A1 of the phase change layer 10 cfrom the amorphous state to the original crystal state, it may be calleda set current. The second phase change current I2 may be a pulsecurrent. An intensity of the second phase change current I2 may be lowerthan that of the first phase change current I1. An applying time of thesecond phase change current I2 may be equal to or longer than that ofthe first phase change current I1.

While the second phase change current I2 is applied to the storage node10 as in FIG. 2(c), a resistance of the contact area A1 of the phasechange layer 10 c may be increased, and a temperature of the contactarea A1 may be increased. Because the intensity of the second phasechange current I2 is relatively low and its applying time is relativelylong unlike the case that the first phase change current I1 is applied,a temperature of the contact area A1 may not increase up to the phasechange temperature of the phase change layer 10 c. As such, because thecontact area A1 is heated for a relatively long time at a temperaturelower than the phase change temperature of the phase change layer 10 c,the contact area A1 may change from an amorphous state to a crystalstate so that the phase change layer 10 c may be entirely in a crystalstate.

As described above, the resistance state of the phase change layer 10 cin the conventional PRAM may be determined by the first phase changecurrent I1, for example, a reset current, and the second phase changecurrent I2, for example, a set current. The first phase change currentI1 may be a current to change a phase of the phase change layer 10 cfrom a crystal state to an amorphous state, for example, current togenerate a heat melting the phase change layer 10 c. On the contrary,the second phase change current I2 may be a current to generate a heatfor changing a phase of the phase change layer 10 c, which is in anamorphous state by the first phase change current I1, from an amorphousstate to a crystal state, and may be lower in current intensity than thefirst phase change current I1.

In the conventional PRAM as described above, the first and second phasechange currents 11 and I2 may be applied to the storage node 10 throughthe transistor Tr. An intensity of the first phase change current I1 asa reset current, and an intensity of the second phase change current I2as a set current may all be lower than an intensity of a currentallowable for the transistor Tr. As described above, because the firstphase change current I1 of the first and second phase change currents I1and I2 may be higher, it may be necessary to reduce a reset current notto limit an integration density of a future PRAM. As ways of reducingthe reset current of the conventional PRAM as described above, therehave been proposed methods of reducing a width of the lower electrodecontact layer 10 b, a method of oxidizing the lower electrode contactlayer 10 b, and a method of employing a higher resistance TiAlN layer asthe lower electrode contact layer 10 b.

The methods may provide an effect of reducing the reset current becausethe lower electrode contact layer 10 b may generate joule heat. Becausethe methods also increase the set resistance, a production yield and areliability of the PRAM may be deteriorated.

SUMMARY

Example embodiments provide a storage node and a phase change memorydevice capable of reducing a reset current while preventing or reducingan increase of a set resistance. Example embodiments also provide amethod of operating the phase change memory device. Other exampleembodiments also provide a method of fabricating the phase change memorydevice.

According to example embodiments, a storage node may include a lowerelectrode, a phase change layer on the lower electrode and an upperelectrode on the phase change layer, wherein the lower electrode and theupper electrode are composed of thermoelectric materials having amelting point higher than that of the phase change layer, and havingdifferent conductivity types.

According to example embodiments, a phase change memory device mayinclude a switching element and the storage node of example embodiments,wherein the lower electrode connected to the switching element. Theswitching element may be a transistor type or a diode type.

An upper surface of the lower electrode may have a recessed shape. Alower electrode contact layer may be provided between the lowerelectrode and the phase change layer. A thickness of the phase changelayer may be about 100 nm or less. The lower electrode may be composedof an n-type thermoelectric material, and the upper electrode may becomposed of a p-type thermoelectric material, or the upper electrode maybe composed of an n-type thermoelectric material, and the lowerelectrode may be composed of a p-type thermoelectric material. Seebackcoefficients of the lower electrode, the phase change layer, and theupper electrode may be different from each other.

The n-type thermoelectric material may be one selected from the groupconsisting of n-SiGe; Sb₂Te₃—Bi₂Te₃ (a Sb₂Te₃ content<a Bi₂Te₃ content);a material having GeTe as a main component; a material having SnTe as amain component; a material having PbTe as a main component; a materialhaving TeAgGeSb as a main component. The materials may include a smalleramount of doping materials. The p-type thermoelectric material may beone selected from the group consisting of p-SiGe; Sb₂Te₃—Bi₂Te₃ (aSb₂Te₃ content>a Bi₂Te₃ content); a material having GeTe as a maincomponent; a material having SnTe as a main component; a material havingPbTe as a main component; a material having TeAgGeSb as a maincomponent. The materials may include a smaller amount of dopingmaterials.

The n-type and p-type thermoelectric materials may be materials having astructure of binary skutterudite and an MX₃ composition (M=Co, Rh, orIr; X=P, As, or Sb). The n-type and p-type thermoelectric materials maybe materials having a structure of filled skutterudite and an RT₄X₁₂composition (R=lanthanide element, actinide or alkaline-earth ion; T=Fe,Ru, Os, and X=P, As, or Sb). The n-type and p-type thermoelectricmaterials may be materials having a structure of clathrate and anA₈B₁₆E₃₀ composition with a little doping (A=alkaline earth metal; B=IIIgroup element (Ga, Al); E=Si, Ge, or Sn).

The lower electrode contact layer may be composed of a thermoelectricmaterial having the same conductivity type as that of the lowerelectrode. When seeback coefficients of the lower electrode, the phasechange layer, and the upper electrode are S1, S2 and S3 respectively,S1, S2 and S3 may satisfy one relation selected from the groupconsisting of a relation of S1<S2<S3, a relation of S1<S3<S2, and arelation of S2<S1<S3. In the relation of S1, S2 and S3, S1 and S3 maysatisfy a relation of S3−S1>100 μV/K (K: absolute temperature).

According to example embodiments, a method of operating a phase changememory device may include maintaining a switching element in an on-stateand applying a voltage between an upper electrode and a lower electrodesuch that current flows through a phase change layer, wherein the lowerelectrode and the upper electrode are composed of thermoelectricmaterials having a melting point higher than that of the phase changelayer, and having different conductivity types.

The switching element may be a transistor type or a diode type. Thecurrent may be a reset current to form an amorphous region in the phasechange layer, and the voltage may be a write voltage. The current may bea set current to change an amorphous region existing in the phase changelayer to a crystal state, and the voltage may be an erase voltage. Thematerial characteristics and geometrical characteristics of the lowerelectrode, the phase change layer, and the upper electrode, andadditional elements may be the same as described in the memory device.

According to example embodiments, a method of fabricating a storage nodemay include forming a lower electrode layer covering a conductive plugon a first interlayer insulating layer, forming a second interlayerinsulating layer covering the lower electrode layer on the firstinterlayer insulating layer, exposing the lower electrode layer in thesecond interlayer insulating layer by forming a via hole, filling thevia hole with a layer, forming an upper electrode layer covering thelayer and etching the upper electrode layer. The layer filling the viahole may be a phase change layer. The layer may be a lower electrodecontact layer filling the via hole and a phase change layer formed onthe second interlayer insulating layer, covering the lower electrodecontact layer. Etching the upper electrode layer may further includeetching the layer filling the via hole and the second interlayerinsulating layer and the lower electrode layer.

According to example embodiments, a method of fabricating a phase changememory device may include forming a switching element on a substrate,forming the at least one interlayer insulating layer covering theswitching element on the substrate, exposing the switching element inthe at least one interlayer insulating layer by forming a contact hole,filling the contact hole with a conductive plug on the at least oneinterlayer insulating layer and forming the storage node according toexample embodiments.

In the fabricating method, the switching element may be a transistortype or a diode type. The lower electrode layer and the upper electrodelayer may be respectively composed of thermoelectric materials havingdifferent conductivity types from each other. The lower electrode layer,the phase change layer, and the upper electrode layer may berespectively formed of material layers having different seebackcoefficients from each other. When seeback coefficients of the lowerelectrode layer, the phase change layer, and the upper electrode layermay be S1, S2 and S3 respectively, the lower electrode layer, the phasechange layer, and the upper electrode layer may be respectively formedof material layers such that S1, S2 and S3 satisfy one relation of arelation of S1<S2<S3, a relation of S1<S3<S2, and a relation ofS2<S1<S3. In the relation of S1, S2 and S3, S1 and S3 may satisfy arelation of S3−S1>100 μV/K (K: absolute temperature).

The lower electrode layer may be composed of an n-type thermoelectricmaterial layer, and the upper electrode layer may be composed of ap-type thermoelectric material layer, or the upper electrode layer maybe composed of an n-type thermoelectric material layer, and the lowerelectrode layer may be composed of a p-type thermoelectric materiallayer.

The filling of the via hole with the phase change layer may compriseforming a phase change material layer filling the via hole on the secondinterlayer insulating layer; and polishing an upper surface of the phasechange material layer until the second interlayer insulating layer isexposed. After polishing, the method may further comprise lowering aheight of an upper surface of the second interlayer insulating layerthan that of an upper surface of the polished phase change materiallayer; and polishing the upper surface of the polished phase changematerial layer until the second interlayer insulating layer is exposed.

According to other example embodiments, there is provided a method offabricating a phase change memory device comprising forming a switchingelement on a substrate; forming a first interlayer insulating layercovering the switching element on the substrate; forming a contact holeexposing the switching element in the first interlayer insulating layer;filling the contact hole with a conductive plug; forming a lowerelectrode covering the conductive plug on the first interlayerinsulating layer; forming a second interlayer insulating layer coveringthe lower electrode on the first interlayer insulating layer; forming avia hole exposing the lower electrode in the second interlayerinsulating layer; filling the via hole with a lower electrode contactlayer; sequentially forming a phase change layer covering the lowerelectrode contact layer and an upper electrode layer on the secondinterlayer insulating layer; and sequentially etching the upperelectrode layer and the phase change layer, in which the lower electrodecontact layer and the upper electrode layer may be respectively composedof thermoelectric materials having different conductivity types fromeach other.

In the fabricating method, when seeback coefficients of the lowerelectrode contact layer, the phase change layer, and the upper electrodelayer may be S1, S2 and S3 respectively, the lower electrode contactlayer, the phase change layer, and the upper electrode layer may berespectively formed of material layers such that S1, S2 and S3 satisfyone relation of a relation of S1<S2<S3, a relation of S1<S3<S2, and arelation of S2<S1<S3. In the relation of S1, S2 and S3, S1 and S3 maysatisfy a relation of S3−S1>100 μV/K (K: absolute temperature).

According to example embodiments, a reset current may be reduced inaccordance with an increased amount of Peltier heat by Peltier effect.Because an allowable current for a transistor may be reduced, a size ofthe transistor may be further scaled down, thereby providing an effectof increasing an integration density of a PRAM. According to exampleembodiments, the reduction of the reset current may be caused by Peltierheat, and may not be related with a size reduction of the lowerelectrode contact layer. According to example embodiments, anintegration density of a PRAM may be increased without an increase of aset resistance.

BRIEF DESCRIPTION OF THE DRAWINGS

Example embodiments will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings. FIGS. 1-21 represent non-limiting, example embodiments asdescribed herein.

FIG. 1 is a diagram illustrating a conventional PRAM;

FIGS. 2(a)-2(c) are diagrams illustrating a method of operating the PRAMof FIG. 1;

FIG. 3 is a diagram illustrating a phase change memory device accordingto example embodiments;

FIG. 4 is a diagram illustrating that an upper surface of a phase changelayer of the memory device of FIG. 3 is recessed;

FIG. 5 is a diagram illustrating a phase change memory device accordingto example embodiments;

FIGS. 6(a)-6(b) illustrate diagrams of a storage node representing amemory device of example embodiments used in an experiment with exampleembodiments and a storage node of a conventional memory device used forcomparison;

FIGS. 7(a)-9(c) are diagrams illustrating a method of operating a phasechange memory device according to example embodiments;

FIGS. 10-17 are diagrams illustrating a method of fabricating a memorydevice according to example embodiments in accordance with processingsequences; and

FIGS. 18-21 are diagrams illustrating a method of fabricating a memorydevice according to other example embodiments in accordance withprocessing sequences.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

Example embodiments will now be described more fully hereinafter withreference to the accompanying drawings, in which example embodiments areshown. Example embodiments may, however, be embodied in many differentforms and should not be construed as being limited to the embodimentsset forth herein. Rather, these embodiments are provided so that thisdisclosure will be thorough and complete, and will fully convey thescope of example embodiments to those skilled in the art. Like numbersrefer to like elements throughout the specification.

Hereinafter, a phase change memory device, and methods of operating andfabricating the same according to example embodiments will be explainedin detail with reference to attached drawings. In the drawings, thethicknesses of layers and regions are exaggerated for clarity.

It will be understood that when an element or layer is referred to asbeing “on,” “connected to” or “coupled to” another element or layer, itcan be directly on, connected or coupled to the other element or layeror intervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on,” “directly connected to”or “directly coupled to” another element or layer, there are nointervening elements or layers present. Like reference numerals refer tolike elements throughout. As used herein, the term “and/or” includes anyand all combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, third etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another region, layer or section. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of example embodiments.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of exampleembodiments. As used herein, the singular forms “a,” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises” and/or “comprising,” when used in this specification,specify the presence of stated features, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,elements, components, and/or groups thereof.

Example embodiments are described herein with reference tocross-sectional illustrations that are schematic illustrations ofexample embodiments (and intermediate structures). As such, variationsfrom the shapes of the illustrations as a result, for example, ofmanufacturing techniques and/or tolerances, are to be expected. Thus,example embodiments should not be construed as limited to the particularshapes of regions illustrated herein but are to include deviations inshapes that result, for example, from manufacturing. For example, animplanted region illustrated as a rectangle will, typically, haverounded or curved features and/or a gradient of implant concentration atits edges rather than a binary change from implanted to non-implantedregion. Likewise, a buried region formed by implantation may result insome implantation in the region between the buried region and thesurface through which the implantation takes place. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the actual shape of a region of a device andare not intended to limit the scope of example embodiments.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which example embodiments belong. Itwill be further understood that terms, such as those defined in commonlyused dictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

A phase change memory device according to example embodiments will beexplained. Referring to FIG. 3, first and second impurity regions S1 andD1 doped with conductive impurities, for example, n-type impurities, maybe provided in a substrate 40 of the example embodiment illustrated inFIG. 3 with a predetermined distance. The substrate 40 may be, forexample, a p-type silicon substrate. The first and second impurityregions S1 and D1 may have various shapes. One of the first and secondimpurity regions S1 and D1, for example, the first impurity region S1may be a source region, and the other one may be a drain region. A gateoxide layer 42 may be disposed on the substrate 40 between the first andsecond impurity regions S1 and D1, and a gate electrode 44 may bedisposed on the gate oxide layer 42.

The substrate 40, the first and second impurity regions S1 and D1, andthe gate electrode 44 may constitute a field effect transistor. A firstinterlayer insulating layer 47 may be disposed on the substrate 40 tocover the transistor. A contact hole 48 may be formed in the firstinterlayer insulating layer 47 to expose the first impurity region S1.The contact hole 48 may be formed at the position exposing the secondimpurity region D1 instead of the first impurity region S1. The contacthole 48 may be filled with a conductive plug 50. A lower electrode 52 amay be disposed on the first interlayer insulating layer 47 to cover anexposed upper surface of the conductive plug 50. The lower electrode 52a may be an electrode, which is composed of an n-type thermoelectricmaterial having a higher melting point than that of a phase change layer56 to be formed and having a first seeback coefficient Si.

The n-type thermoelectric material may be one selected from the groupconsisting of n-SiGe, Sb₂Te₃—Bi₂Te₃, a material having GeTe as a maincomponent, a material having SnTe as a main component, a material havingPbTe as a main component and/or a material having TeAgGeSb as a maincomponent. The materials may include a relatively small amount of adoping material. The n-type thermoelectric material may be a materialhaving a structure of binary skutterudite and an MX₃ composition (M=Co,Rh and/or Ir; X=P, As and/or Sb). The n-type thermoelectric material maybe a material having a structure of filled skutterudite, and an RT₄X₁₂composition (R=lanthanide element, actinide or alkaline-earth ion; T=Fe,Ru, Os, and X=P, As, or Sb).

The n-type thermoelectric material may be a material having a structureof clathrate, and an A₈B₁₆E₃₀ composition with a relatively small amountof doping (A=alkaline earth metal; B=III group element (Ga, Al); E=Si,Ge, or Sn). When the lower electrode 52 a is an electrode which iscomposed of a Sb₂Te₃—Bi₂Te₃ material as an example of the n-typethermoelectric material, a Sb₂Te₃ content of the lower electrode 52 amay be lower than a Bi₂Te₃ content. A second interlayer insulating layer54 may be disposed on an upper surface of the lower electrode 52 a. Avia hole h1 may be formed in the second interlayer insulating layer 54to expose a portion of the lower electrode 52 a. The via hole hi may befilled with the phase change layer 56. The phase change layer 56 may bea material having a second seeback coefficient S2, for example, GSTlayer. The first seeback coefficient S1 may be higher or lower than thesecond seeback coefficient S2. Because the via hole h1 is filled withthe phase change layer 56, a depth of the via hole h1 may determine athickness of the phase change layer 56. Because the thickness of thephase change layer 56 may be about 100 nm or less, for example, about 20nm, the via hole h1 may be formed with a thickness of the above.

An upper electrode 58 a may be disposed on the second interlayerinsulating layer 54 to cover the exposed portion of the phase changelayer 56 filling the via hole h1. The upper electrode 58 a may be anelectrode, which is composed of a p-type thermoelectric material havinga higher melting point than that of the phase change layer 56 and athird seeback coefficient S3. The p-type thermoelectric material may beone selected from the group consisting of, for example, p-SiGe,Sb₂Te₃—Bi₂Te₃, a material having GeTe as a main component, a materialhaving SnTe as a main component, a material having PbTe as a maincomponent and a material having TeAgGeSb as a main component. Thematerials may have a smaller amount of a doping material.

The p-type thermoelectric material may be a material having a structureof binary skutterudite and an MX₃ composition (M=Co, Rh, or Ir; X=P, As,or Sb). The p-type thermoelectric material may be a material having astructure of filled skutterudite, and an RT₄X₁₂ composition(R=lanthanide element, actinide and/or alkaline-earth ion; T=Fe, Ru, Os,and X=P, As, or Sb). The p-type thermoelectric material may be amaterial having a structure of clathrate, and an A₈B₁₆E₃₀ compositionwith a relatively small amount of doping (A=alkaline earth metal; B=IIIgroup element (Ga, Al); E=Si, Ge, or Sn).

When the upper electrode 58 a is an electrode which is composed of aSb₂Te₃—Bi₂Te₃ material as an example of the p-type thermoelectricmaterial, a Sb₂Te₃ content of the upper electrode 58 a may be more thana Bi₂Te₃ content. The third seeback coefficient S3 may be higher thanthe first seeback coefficient S1 (S3>S1), but the third seebackcoefficient S3 may be higher or lower than the second seebackcoefficient S2 (S3>S2 or S3<S2). When the third seeback coefficient S3is higher than the first seeback coefficient S1, the first and thirdseeback coefficients S1 and S3 may satisfy a following formula.S3−S1>100 μV/K, (K: absolute temperature)  <Formula 1>

When the lower electrode 52 a is an electrode, which is composed of ann-type thermoelectric material, and the upper electrode 58 a is anelectrode, which is composed of a p-type thermoelectric material, thefirst and third seeback coefficients S1 and S3 may satisfy formula 1,and the first through third seeback coefficients S1 through S3 maysatisfy a first relation (S1<S2<S3), but the first through third seebackcoefficients S1 through S3 may satisfy a second relation (S2<S1<S3)and/or a third relation (S1<S3<S2).

Types of the thermoelectric materials of the lower electrode 52 a andthe upper electrode 58 a may be opposite to each other. For example, thelower electrode 52 a may be a p-type thermoelectric material electrode,and the upper electrode 58 a may be an n-type thermoelectric materialelectrode. As such, when the thermoelectric materials of the lowerelectrode 52 a and the upper electrode 58 a have opposite types, thereference numeral S1 may show a seeback coefficient of the upperelectrode 58 a, and the reference numeral S3 may show a seebackcoefficient of the lower electrode 52 a. The position where Peltiereffect is generated may be different from that before the types of thethermoelectric materials to form the lower electrode 52 a and the upperelectrode 58 a may be opposite to each other. If a direction of thecurrent flowing through the lower electrode 52 a and the upper electrode58 a may change reversely while the conductivity types of thethermoelectric materials to respectively form the lower electrode 52 aand the upper electrode 58 a may be opposite to each other, the positionwhere Peltier effect is generated may not be changed.

Referring to FIG. 4, an upper surface 56 s of the phase change layer 56filling the via hole h1 may be a recessed surface not a flat surfacelike the second interlayer insulating layer 54. A portion of the upperelectrode 58 a contacting the phase change layer 56 may have a shapeextending toward the via hole h1, for example, a downwardly-convexshape. A phase change memory device according to example embodimentswill be explained. Because a structure of the example embodiment in FIG.5 is mostly similar to that of the example embodiment in FIG. 3, afollowing description may be confined to the points that the exampleembodiment in FIG. 5 may be different from the example embodiment inFIG. 3.

Referring to FIG. 5, a lower electrode 60 may be disposed on a firstinterlayer insulating layer 46 covering a transistor to cover an exposedupper surface of a conductive plug 50. The lower electrode 60 may alsofunction as a pad layer. The lower electrode 60 may be an electrodewhich is composed of the same material as that of the lower electrode 52a in example embodiment in FIG. 3. A second interlayer insulating layer62 may be disposed on the first interlayer insulating layer 46 to coverthe lower electrode 60. The second interlayer insulating layer 62 may becomposed of the same insulating material as that of the first interlayerinsulating layer 46. A contact hole h2 may be formed in the secondinterlayer insulating layer 62 to expose an upper surface of the lowerelectrode 60.

The contact hole h2 may be filled with a lower electrode contact layer64. The lower electrode contact layer 64 may be composed of the samematerial as that of the lower electrode 60. A phase change layer 56 maybe disposed on the second interlayer insulating layer 62 to cover anexposed upper surface of the lower electrode contact layer 64, and anupper electrode 58 a may be disposed on the phase change layer 56. Thephase change layer 56 and the upper electrode 58 a may be the same asthose described in the example embodiment in FIG. 3.

A comparison experiment may be performed to check reset currentcharacteristics of a memory device according to example embodiments asdescribed above. In this experiment, a phase change memory deviceaccording to example embodiments may be fabricated to have the samestructure as that of the example embodiment illustrated in FIG. 3, and aconventional memory device to compare the memory device of exampleembodiments may be fabricated such that lower and upper electrodes maybe composed of TiAlN.

FIG. 6(a) illustrates a storage node of the memory device of exampleembodiments used in this experiment and FIG. 6(b) illustrates a storagenode of the conventional memory device. Referring to FIG. 6(a) and FIG.6(b), the storage node of example embodiments and the conventionalstorage node may be the same in their structures, but different in thematerials of the upper and lower electrodes. In the storage nodes, phasechange layers P1 and P11 may be all formed of GST layers, and athickness t and a diameter D may be about 20 nm and about 50 nm,respectively.

If examining change of the storage node of example embodiments in thisexperiment, when a current flowing between upper and lower electrodes T1and B1 is about 0.69 mA after applying a voltage between the upper andlower electrodes T1 and B1, a portion of a phase change layer S2contacting the upper and lower electrodes T1 and B1 may be changed to anamorphous state. If examining change of the conventional storage node inthis experiment, when a current flowing between upper and lowerelectrodes T11 and B11 is about 0.79 mA after applying a voltage betweenthe upper and lower electrodes T11 and B11, a portion of a phase changelayer P11 contacting the upper and lower electrodes T11 and B11 may bechanged to amorphous state.

From the experiment, it may be acknowledged that a reset current of thestorage node of example embodiments may be lower than a reset current ofthe conventional storage node. The experiment result coincides with theexpectation that the phase change layer of the memory device of exampleembodiments may be changed to an amorphous state at a reset currentlower than that of the conventional memory device because a heat due toPeltier effect may be generated in addition to a joule heat. BecausePeltier effect has no relation with geometrical shapes of the upper andlower electrodes contacting the phase change layer, a side effect (e.g.,an increase of a set resistance related with Peltier effect) may not begenerated in the memory devices of example embodiments.

A method of operating a memory device according to example embodimentsdescribed above will be explained in reference to FIGS. 7(a)-9(c). As atransistor is always in an on-state in the operating method of exampleembodiments, the transistor may not be illustrated in FIGS. 7(a)-9(c).FIGS. 7(a)-9(c) illustrate a method of operating the example embodimentillustrated in FIG. 3, and FIG. 7(a)-7(c) illustrate an operating methodwhen a relation between seeback coefficients of a lower electrode 52 a,a phase change layer 56, and an upper electrode 58 a of the exampleembodiment illustrated in FIG. 3, for example, first through threeseeback coefficients S1 through S3 may be S1<S3<S2. FIGS. 8(a)-8(c)illustrate an operating method when a relation between the first throughthree seeback coefficients S1 through S3 is S2<S1<S3. FIGS. 9(a)-9(c)illustrate an operating method when a relation between the first throughthree seeback coefficients S1 through S3 is S1<S2<S3.

<Write>

Referring to FIG. 7, as shown in FIG. 7(a), a write voltage may beapplied between the upper and lower electrodes 58 and 52 for apredetermined time, for example, dozens of nanoseconds such that a resetcurrent Irs may be flowed to the phase change layer 56 having a crystalstate. The reset current Irs may be a pulse current having apredetermined height I1 h, and smaller in intensity than a conventionalreset current. When the write voltage is applied between the lowerelectrode 52 a and the upper electrode 58 a in accordance with arelation (S1<S3<S2) between the seeback coefficients of the lowerelectrode 52 a, the phase change layer 56, and the upper electrode 58 a,a temperature of the portion of the phase change layer 56 contacting thelower electrode 52 a may be momentarily changed to a phase changetemperature or higher. The portion of the phase change layer 56contacting the lower electrode 52 a may be changed to an amorphousregion 80 as illustrated in FIG. 7(b). When the portion of the phasechange layer 56 is changed to the amorphous region 80, an electricalresistance of the phase change layer 56 may increase. When the amorphousregion 80 is formed as above, and the electrical resistance of the phasechange layer 56 increases, bit data 1 may be recorded in the exampleembodiment illustrated in FIG. 3.

When the amorphous region 80 of the phase change layer 56 has a crystalstate, and thus, the entire phase change layer 56 comes to have acrystal state, bit data 0 may be recorded in the example embodimentillustrated in FIG. 3. In order to change the amorphous region 80 of thephase change layer 56 into a crystal state, a predetermined voltage maybe applied between the lower electrode 58 a and the upper electrode 52 asuch that a set current Is may be flowed to the phase change layer 56 ina state that the amorphous region 80 exists in the phase change layer 56as illustrated in FIG. 7(b). The set current Is as a pulse current mayhave a current intensity I2 h, which is smaller than that of the resetcurrent Irs. An applying time of the set current Is may be longer thanthat of the reset current Irs.

When the set current Is is applied, the amorphous region 80 of the phasechange layer 56 may be changed to a crystal state, and thus, the entirephase change layer 56 may be changed to a crystal state as illustratedin FIG. 7(c). The respective states of the phase change layer 56 inFIGS. 7(c) and (a) may be the same. The process of applying the setcurrent Is to the phase change layer 56 illustrated in FIG. 7(b) may beconsidered as a process of erasing bit data 1 recorded in the phasechange layer 56, or as a process of recording bit data 0 to the phasechange layer 56.

Referring to FIGS. 8(a)-8(c), when a relation between seebackcoefficients of the lower electrode 52 a, the phase change layer 56, andthe upper electrode 58 a, for example, first through three seebackcoefficients S1 through S3 is S2<S1<S3, and when the same write voltageas that in the operating method illustrated in FIGS. 7(a)-7(c) isapplied between the lower electrode 52 a and the upper electrode 58 a, atemperature of the portion of the phase change layer 56 contacting theupper electrode 58 a may be momentarily changed to a phase changetemperature or higher as illustrated in FIG. 8(a), so that the portionof the phase change layer 56 contacting the upper electrode 58 a maychange to an amorphous region 90 as illustrated in FIG. 8(b). Any changemay not be found in the portion of the phase change layer 56 contactingthe lower electrode 52 a as illustrated in FIG. 8(c).

As above, when the seeback coefficients S1, S2, and S3 of the lowerelectrode 52 a, the phase change layer 56, and the upper electrode 58 asatisfy a relation of S2<S1<S3, operating characteristics of the exampleembodiment illustrated in FIG. 3 may be the same as the characteristicsillustrated in FIGS. 7(a)-7(c) except for the position of the amorphousregion 90 formed in the phase change layer 56 during the operatingprocess of the example embodiment illustrated in FIG. 3. As illustratedin FIGS. 7(a)-7(c) and 8(a)-8(c), even though positions where theamorphous regions are formed in the phase change layer 56 are different,current-resistance characteristics of the example embodiment illustratedin FIG. 3 may not be changed. The operating methods illustrated in FIGS.7(a)-7(c) and 8(a)-8(c) may be substantially same.

Referring to FIGS. 9(a)-9(c), when the seeback coefficients S1, S2, andS3 of the lower electrode 52 a, the phase change layer 56, and the upperelectrode 58 a satisfy a relation of S1<S2<S3, and when the same voltageas the write voltage applied in the operating method of FIGS. 7(a)-7(c)may be applied between the lower electrode 52 a and the upper electrode58 a as illustrated in FIG. 9(a), first and second amorphous regions 100and 110 may be formed in the phase change layer 56 as illustrated inFIG. 9(b). The first amorphous region 100 may be formed at a positionwhere the phase change layer 56 contacts the lower electrode 52 a, andthe second amorphous region 110 may be formed at a position where thephase change layer 56 contacts the upper electrode 58 a.

As such, a resistance of the phase change layer 56 when amorphousregions 100 and 110 exist at two positions of the phase change layer 56may be higher than that of the phase change layer 56 when the amorphousregion 80 or 90 exists only at one position of the phase change layer 56as illustrated in FIGS. 7(a)-7(c) or FIGS. 8(a)-8(c). In the operatingmethod of the example embodiment illustrated in FIG. 3 and illustratedin FIGS. 9(a)-9(c), a difference between a resistance of the phasechange layer 56 when the first and second amorphous regions 100 and 110may be formed in the phase change layer 56, for example, when bit data 1is recorded, and a resistance of the phase change layer 56 when anamorphous region does not exist in the phase change layer 56, forexample, when bit data 0 is recorded, may be greater than a resistancedifference in the operating method illustrated in FIGS. 7(a)-7(c) orFIGS. 8(a)-8(c).

<Write>

A read voltage may be applied between the upper electrode 58 a and thelower electrode 52 a in a writing process such that a current may notchange a phase of the amorphous region formed in the phase change layer56, for example, a current lower than a set current may be flowedthrough the phase change layer 56 as illustrated in FIG. 9(c). The readvoltage may be intended to measure a resistance of the phase changelayer 56. The resistance of the phase change layer 56 measured byapplying the read voltage may be compared with a reference resistance.As a result of the comparison, when the measured resistance of the phasechange layer 56 is higher than the reference resistance, bit data 1 maybe recorded in the memory device. When the measured resistance of thephase change layer 56 is lower than the reference resistance, bit data 0may be recorded in the memory device.

A method of fabricating a phase change memory device according toexample embodiments will be explained. A method of fabricating theexample embodiment illustrated in FIG. 3 will be explained. Referring toFIG. 10, a substrate 40 may be divided into an active region wheredevice elements will be formed, and a field region where device elementswill not be formed. The substrate 40 may be formed of a siliconsubstrate including predetermined conductive impurities, for example,p-type impurities. A field oxide layer (not shown) may be formed in thefield region to isolate elements. A gate oxide layer 42 and a gateelectrode 44 may be sequentially formed on a predetermined portion ofthe active region of the substrate 40. The active region may be dopedwith conductive impurities having a conductivity type opposite to thatof the impurities doping the substrate 40, for example, n-typeimpurities, using the gate electrode 44 as a mask.

First and second impurity regions S1 and D1 may be formed with the gateelectrode 44 disposed therebetween. The first and second impurityregions S1 and D1 may be formed with a lightly doped drain (LDD) type ofimpurities. One of the first and second impurity regions S1 and D1 maybe a source region, and the other one thereof may be a drain region. Afield effect transistor may be formed in the substrate 40. The fieldeffect transistor may be a switching element, and may be replaced with adifferent switching element, for example, a diode.

A first interlayer insulating layer 46 covering the transistor may beformed on the substrate 40, and a contact hole 48 may be formed in thefirst interlayer insulating layer 46 to expose the first impurity regionS1. The contact hole 48 may be formed at a position where the secondimpurity region D1 is exposed instead of the first impurity region S1.After a conductive material (not shown) filling the contact hole 48 isformed on the first interlayer insulating layer 46, an upper surface ofthe conductive material may be planarized until the first interlayerinsulating layer 46 is exposed. The contact hole 48 may be filled with aconductive plug 50.

Referring to FIG. 11, a lower electrode layer 52 may be formed on thefirst interlayer insulating layer 46 to cover an exposed upper surfaceof the conductive plug 50. The lower electrode layer 52 may be formed ofan n-type thermoelectric material layer having a melting point higherthan that of a phase change layer 56 to be formed later, and having afirst seeback coefficient S1. The n-type thermoelectric material layermay be one selected from the group consisting of an n-SiGe layer, aSb₂Te₃—Bi₂Te₃ layer, a material layer having GeTe as a main component, amaterial layer having SnTe as a main component, a material layer havingPbTe as a main component and a material layer having TeAgGeSb as a maincomponent. If necessary, the material layers may be doped with arelatively small amount of a doping material.

The n-type thermoelectric material layer may be formed of a materiallayer having a structure of binary skutterudite and an MX₃ composition(M=Co, Rh or Ir; X=P, As or Sb). The n-type thermoelectric materiallayer may be formed of a material layer having a structure of filledskutterudite and an RT₄X₁₂ composition (R=lanthanide element, actinideor alkaline-earth ion; T=Fe, Ru or Os and X=P, As or Sb). The n-typethermoelectric material layer may be formed of a material layer having astructure of clathrate, and an A₈B₁₆E₃₀ composition with a little doping(A=alkaline earth metal; B=III group element (Ga, Al); E=Si, Ge or Sn).

In the material layers of the n-type thermoelectric material layer, theSb₂Te₃—Bi₂Te₃ layer may have a Sb₂Te₃ content lower than a Bi₂Te₃content. The lower electrode layer 52 may be formed of a p-typethermoelectric material layer. After the lower electrode layer 52 isformed, a second interlayer insulating layer 54 may be formed on thelower electrode layer 52. The second interlayer insulating layer 54 maybe formed of, for example, a silicon oxynitride (SiON) layer. Athickness of the phase change layer to be formed in a subsequent processmay be substantially determined by a thickness of the second interlayerinsulating layer 54. The second interlayer insulating layer 54 may beformed by considering the thickness of the phase change layer. Forexample, the second interlayer insulating layer 54 may be formed with athickness of about 100 nm or smaller, and may be formed with a thicknessof about 20 nm. A via hole h1 may be formed in the second interlayerinsulating layer 54 to expose the lower electrode layer 52. The via holeh1 may be formed over the contact hole 48.

Referring to FIG. 12, a phase change layer 56 may be formed on thesecond interlayer insulating layer 54 to fill the via hole h1. An uppersurface of the phase change layer 56 may be polished using apredetermined polishing method, for example, a chemical mechanicalpolishing (CMP) method or an etch-back method. The polishing method maybe performed until the second interlayer insulating layer 54 is exposed.As a result of the polishing, the portion of the phase change layer 56formed around the via hole h1 may be removed, and the phase change layer56 may remain only inside the via hole h1. FIG. 13 illustrates theresult. The phase change layer 56 may be formed of a material layerhaving a melting point lower than that of the lower electrode layer 52and having a second seeback coefficient S2, for example, a Ge₂Sb₂Te₅layer or a doped Ge₂Sb₂Te₅ layer.

Referring to FIG. 14, an upper electrode layer 58 may be formed on thesecond interlayer insulating layer 54 to cover the exposed portion ofthe phase change layer 56 filling the via hole h1. The upper electrodelayer 58 may be formed of a p-type thermoelectric material layer havinga melting point higher than that of the phase change layer 56 and havinga third seeback coefficient S3.

The p-type thermoelectric material layer may be formed of one selectedfrom the group consisting of a p-SiGe layer, a Sb₂Te₃—Bi₂Te₃ layer, amaterial layer having GeTe as a main component, a material layer havingSnTe as a main component, a material layer having PbTe as a maincomponent and/or a material layer having TeAgGeSb as a main component.If necessary during the processes of forming the p-type thermoelectricmaterial layer, the material layers used for the p-type thermoelectricmaterial layer may be doped with a relatively small amount of a dopingmaterial. The p-type thermoelectric material layer may be formed of amaterial layer having a structure of binary skutterudite and an MX₃composition (M=Co, Rh or Ir; X=P, As or Sb).

The p-type thermoelectric material layer may be formed of a materiallayer having a structure of filled skutterudite, and an RT₄X₁₂composition (R=lanthanide element, actinide or alkaline-earth ion; T=Fe,Ru, Os, and X=P, As or Sb). The p-type thermoelectric material layer maybe formed of a material layer having a structure of clathrate, and anA₈B₁₆E₃₀ composition with a little doping (A=alkaline earth metal; B=IIIgroup element (Ga, Al); E=Si, Ge, or Sn). When the upper electrode layer58 is formed of a Sb₂Te₃—Bi₂Te₃ layer, a Sb₂Te₃ content may be greaterthan a Bi₂Te₃ content. The third seeback coefficient S3 may be higherthan the first seeback coefficient S1 (S3>S1), but the third seebackcoefficient S3 may be higher or lower than the second seebackcoefficient S2 (S3>S2 or S3<S2). When the third seeback coefficient S3is higher than the first seeback coefficient S1, the first and thirdseeback coefficients S1 and S3 may satisfy Formula 1.

The lower electrode layer 52 may be formed of the n-type thermoelectricmaterial layer, and the upper electrode layer 58 may be formed of thep-type thermoelectric material layer, the first and third seebackcoefficients S1 and S3 may satisfy Formula 1, and the first throughthird seeback coefficients S1-S3 may satisfy a first relation(S1<S2<S3), or may satisfy a second relation (S2<S1<S3) or a thirdrelation (S1<S3<S2).

The lower electrode layer 52 may be formed of the p-type thermoelectricmaterial layer, and the upper electrode layer 58 may be formed of then-type thermoelectric material layer. If the upper electrode layer 58and the lower electrode layer 52 satisfy the condition that they may berespectively formed of thermoelectric material layers having oppositeconductivity types, one of the upper electrode layer 58 and the lowerelectrode layer 52 may be formed of any one of the n-type thermoelectricmaterial layer and the p-type thermoelectric material layer.

When the lower electrode layer 52 is formed of any one of the p-typethermoelectric material layers, and the upper electrode layer 58 isformed of any one of the n-type thermoelectric material layers, thereference numeral S1 in the relation of the seeback coefficients mayindicate a seeback coefficient of the upper electrode layer 58 and thereference numeral S3 may indicate a seeback coefficient of the lowerelectrode layer 52. The position where Peltier effect may be generatedmay be different from that before the types of the thermoelectricmaterial layers to form the lower electrode layer 52 and the upperelectrode layer 58 may be opposite to each other. If a direction of thecurrent flowing through the lower electrode layer 52 and the upperelectrode layer 58 during an operating process is changed reversely, theposition where Peltier effect is generated may not be changed.

After the upper electrode layer 58 is formed, a photosensitive layerpattern (not shown) may be formed on a predetermined portion of theupper electrode layer 58. The photosensitive layer pattern may be formedat a position to cover the via hole 56. The upper electrode layer 58,the second interlayer insulating layer 54, and the lower electrode layer52 may be sequentially etched using the photosensitive layer pattern asan etch mask. After the etching, the photosensitive layer pattern may beremoved. The example embodiment illustrated in FIG. 3 may be fabricated.During the process of planarizing the phase change layer 56 of FIG. 12,the portion of the phase change layer 56 filling the via hole h1 may beformed such that its upper surface may be recessed as illustrated inFIG. 15, and then, in this state as above, the upper electrode layer 58may be formed on the second interlayer insulating layer 54 to fill therecessed upper surface of the via hole h1 as illustrated in FIG. 16.After the recessed upper surface of the phase change layer 56 fillingthe via hole in the state illustrated in FIG. 15, the upper electrodelayer 56 may be formed on the second interlayer insulating layer 54.

A portion of the second interlayer insulating layer 54 around the phasechange layer 56 having a recessed upper surface may be removed asillustrated in FIG. 17, so that a height of the upper surface of thesecond interlayer insulating layer 54 may be lower than that of therecessed upper surface of the phase change layer 56. In order to achievethe result, the resultant structure illustrated in FIG. 15 may bewet-etched using an etchant having a higher etch selectivity withrespect to the second interlayer insulating layer 54 than that withrespect to the phase change layer 56.

As above, because the height of the upper surface of the secondinterlayer insulating layer 54 is lower, the phase change layer 56filling the via hole h1 may have a protruded shape as illustrated inFIG. 17. In this state, the protruded portion of the phase change layer56 may be polished and removed. The upper surface of the phase changelayer 56 may become flat as illustrated in FIG. 13. The upper electrodelayer 58 may be formed on the second interlayer insulating layer 54 asillustrated in FIG. 14.

A method of fabricating the memory device according to exampleembodiments will be explained in reference to FIGS. 18-21. Referring toFIG. 18, a contact hole 48 may be formed in a first interlayerinsulating layer 46 by the method of fabricating the example embodimentillustrated in FIG. 3, and the contact hole 48 may be filled with aconductive plug 50. A lower electrode 60 may be formed on the firstinterlayer insulating layer 46. The lower electrode 60 may be formed ofthe thermoelectric material layer to form the lower electrode layer 52as explained in the method of fabricating the example embodimentillustrated in FIG. 3.

Referring to FIG. 19, a second interlayer insulating layer 62 may beformed on the first interlayer insulating layer 42 to cover the lowerelectrode 60. The second interlayer insulating layer 62 may be composedof the same material as that of the first interlayer insulating layer46. After a via hole h2 exposing the lower electrode 60 is formed in thesecond interlayer insulating layer 62, the via hole h2 may be filledwith a lower electrode contact layer 64 as illustrated in FIG. 20. Anupper surface of the lower electrode contact layer 64 may be formedrecessed or flat during the process of forming the lower electrodecontact layer 64. The lower electrode contact layer 64 may be composedof a thermoelectric material having the same characteristics as that ofthe lower electrode 60. The lower electrode contact layer 64 may havethe same seeback coefficient as that of the lower electrode 60.

A phase change layer 56 may be formed on the second interlayerinsulating layer 62 to cover an exposed surface of the lower electrodecontact layer 64 as illustrated in FIG. 21, and an upper electrode layer58 may be formed on the phase change layer 56. The phase change layer 56and the upper electrode layer 58 may be the same as explained in themethod of fabricating the example embodiment illustrated in FIG. 3.After the upper electrode layer 58 is formed, a photosensitive layerpattern (not shown) may be formed on the upper electrode layer 58 toconfine a storage node region, and using the photosensitive layerpattern as an etch mask, the upper electrode layer 58 and the phasechange layer 56 may be sequentially etched. After the etching, thephotosensitive layer pattern may be removed. The example embodimenthaving the structure as illustrated in FIG. 5 may be fabricated.

As many descriptions have been made in detail as above, but they may beinterpreted as example embodiments rather than confining the scope ofexample embodiments. For example, it may be understood to those skilledin this art that the lower electrode 52 a, the lower electrode contactlayer 64, and the upper electrode 58 a may be formed of thermoelectricmaterials other than the p-type and n-type thermoelectric materials asdescribed above. The phase change layer 56 may be formed of a materiallayer other than the GST layer. A method of operating the phase changememory device may be performed by reversely applying the directions ofthe reset current and the set current. The scope of example embodimentsmay not be limited to the embodiments as described above, but may bedefined by the following claims.

As described above, in the phase change memory device of exampleembodiments, the lower electrode 52 a and the upper electrode 58 a ofthe storage node, or the lower electrode contact layer 64 and the upperelectrode 58 a may be composed of thermoelectric materials havingopposite conductivity types. The seeback coefficients S1, S2, and S3 ofthe lower electrode 52 a (or the lower electrode contact layer 64), thephase change layer 56, and the upper electrode 58 a satisfy a firstrelation (S1<S2<S3), a second relation (S2<S1<S3), and a third relation(S1<S3<S2).

Peltier heat may be generated at the interface between the lowerelectrode 52 a and the phase change layer 56, the interface between theupper electrode 58 a and the phase change layer 56, or the twointerfaces between the upper and lower electrodes and the phase changelayer 56 due to difference of seeback coefficients. A reset current maybe reduced in accordance with an increase of the Peltier heat by exampleembodiments. As an allowable current of the transistor may be reduced,the size of the transistor may be further reduced, which provides aresult of increasing an integration density of the phase change memorydevice. The decrease of the reset current may be caused by the Peltierheat, and may not be related with the size reduction of the lowerelectrode contact layer 64. According to example embodiments, anintegration density of the phase change memory device may be increasedwithout an increase of a set resistance.

While example embodiments have been particularly shown and describedwith reference to example embodiments thereof, it will be understood bythose of ordinary skill in the art that various changes in form anddetails may be made therein without departing from the spirit and scopeof the following claims.

1. A storage node comprising: a lower electrode; a phase change layer onthe lower electrode; and an upper electrode on the phase change layer,wherein the lower electrode and the upper electrode are composed ofthermoelectric materials having a melting point higher than that of thephase change layer, and having different conductivity types.
 2. A phasechange memory device comprising: a switching element; and the storagenode of claim 1, the lower electrode connected to the switching element.3. The phase change memory device of claim 2, wherein the switchingelement is a transistor type or a diode type.
 4. The storage node ofclaim 1, wherein an upper surface of the lower electrode has a recessedshape.
 5. The storage node of claim 1, further comprising: a lowerelectrode contact layer between the lower electrode and the phase changelayer.
 6. The storage node of claim 5, wherein the lower electrodecontact layer is composed of a thermoelectric material having the sameconductivity type as that of the lower electrode.
 7. The storage node ofclaim 1, wherein a thickness of the phase change layer is about 100 nmor less.
 8. The storage node of claim 1, wherein the lower electrode iscomposed of an n-type thermoelectric material and the upper electrode iscomposed of a p-type thermoelectric material.
 9. The storage node ofclaim 8, wherein, when seeback coefficients of the lower electrode, thephase change layer, and the upper electrode are S1, S2 and S3respectively, S1, S2 and S3 satisfy one relation selected from the groupconsisting of a relation of S1<S2<S3, a relation of S1<S3<S2, and arelation of S2<S1<S3.
 10. The storage node of claim 9, wherein in therelation of S1, S2 and S3, S1 and S3 satisfy a relation of S3−S1>100μV/K (K: absolute temperature).
 11. The storage node of claim 8, whereinthe n-type thermoelectric material is one selected from the groupconsisting of n-SiGe; Sb₂Te₃—Bi₂Te₃ (a Sb₂Te₃ content<a Bi₂Te₃ content);a material having GeTe as a main component; a material having SnTe as amain component; a material having PbTe as a main component; a materialhaving TeAgGeSb as a main component; a material having a structure ofbinary skutterudite and an MX₃ composition (M=Co, Rh, or Ir; X=P, As, orSb); a material having a structure of filled skutterudite and an RT₄X₁₂composition (R=lanthanide element, actinide or alkaline-earth ion; T=Fe,Ru, Os, and X=P, As, or Sb); and a material having a structure ofclathrate and an A₈B₁₆E₃₀ composition with a little doping (A=alkalineearth metal; B=III group element (Ga, Al); E=Si, Ge, or Sn).
 12. Thestorage node of claim 8, wherein the p-type thermoelectric material isone selected from the group consisting of p-SiGe; Sb₂Te₃—Bi₂Te₃ (aSb₂Te₃ content>a Bi₂Te₃ content); a material having GeTe as a maincomponent; a material having SnTe as a main component; a material havingPbTe as a main component; a material having TeAgGeSb as a maincomponent; a material having a structure of binary skutterudite and anMX₃ composition (M=Co, Rh, or Ir; X=P, As, or Sb); a material having astructure of filled skutterudite and an RT₄X₁₂ composition (R=lanthanideelement, actinide or alkaline-earth ion; T=Fe, Ru, Os, and X=P, As, orSb); and a material having a structure of clathrate and an A₈B₁₆E₃₀composition with a little doping (A=alkaline earth metal; B=III groupelement (Ga, Al); E=Si, Ge, or Sn).
 13. The storage node of claim 1,wherein the upper electrode is composed of an n-type thermoelectricmaterial, and the lower electrode is composed of a p-type thermoelectricmaterial.
 14. The storage node of claim 13, wherein the n-typethermoelectric material is one selected from the group consisting ofn-SiGe; Sb₂Te₃—Bi₂Te₃ (a Sb₂Te₃ content<a Bi₂Te₃ content); a materialhaving GeTe as a main component; a material having SnTe as a maincomponent; a material having PbTe as a main component; a material havingTeAgGeSb as a main component; a material having a structure of binaryskutterudite and an MX₃ composition (M=Co, Rh, or Ir; X=P, As, or Sb); amaterial having a structure of filled skutterudite and an RT₄X₁₂composition (R=lanthanide element, actinide or alkaline-earth ion; T=Fe,Ru, Os, and X=P, As, or Sb); and a material having a structure ofclathrate and an A₈B₁₆E₃₀ composition with a little doping (A=alkalineearth metal; B=III group element (Ga, Al); E=Si, Ge, or Sn).
 15. Thestorage node of claim 13, wherein the p-type thermoelectric material isone selected from the group consisting of p-SiGe; Sb₂Te₃—Bi₂Te₃ (aSb₂Te₃ content>a Bi₂Te₃ content); a material having GeTe as a maincomponent; a material having SnTe as a main component; a material havingPbTe as a main component; a material having TeAgGeSb as a maincomponent; a material having a structure of binary skutterudite and anMX₃ composition (M=Co, Rh, or Ir; X=P, As, or Sb); a material having astructure of filled skutterudite and an RT₄X₁₂ composition (R=lanthanideelement, actinide or alkaline-earth ion; T=Fe, Ru, Os, and X=P, As, orSb); and a material having a structure of clathrate and an A₈B₁₆E₃₀composition with a little doping (A=alkaline earth metal; B=III groupelement (Ga, Al); E=Si, Ge, or Sn).
 16. The storage node of claim 1,wherein seeback coefficients of the lower electrode, the phase changelayer, and the upper electrode are different from each other.
 17. Amethod of operating a phase change memory device comprising: maintaininga switching element in an on-state; and applying a voltage between anupper electrode and a lower electrode such that current flows through aphase change layer, wherein the lower electrode and the upper electrodeare composed of thermoelectric materials having a melting point higherthan that of the phase change layer, and having different conductivitytypes.
 18. The method of claim 17, wherein the current is a resetcurrent to form an amorphous region in the phase change layer, and thevoltage is a write voltage.
 19. The method of claim 17, wherein thecurrent is a set current to change an amorphous region existing in thephase change layer to a crystal state, and the voltage is an erasevoltage.
 20. A method of fabricating a storage node comprising: forminga lower electrode layer covering a conductive plug on a first interlayerinsulating layer; forming a second interlayer insulating layer coveringthe lower electrode layer on the first interlayer insulating layer;exposing the lower electrode layer in the second interlayer insulatinglayer by forming a via hole; filling the via hole with a layer; formingan upper electrode layer covering the layer; and etching the upperelectrode layer.
 21. The method of claim 20, wherein the layer fillingthe via hole is a phase change layer.
 22. The method of claim 20,wherein the layer is a lower electrode contact layer filling the viahole and a phase change layer formed on the second interlayer insulatinglayer, covering the lower electrode contact layer.
 23. The method ofclaim 20, wherein etching the upper electrode layer further includes:sequentially etching the layer filling the via hole and the secondinterlayer insulating layer and the lower electrode layer.
 24. A methodof fabricating a phase change memory device comprising: forming aswitching element on a substrate; forming the at least one interlayerinsulating layer covering the switching element on the substrate;exposing the switching element in the at least one interlayer insulatinglayer by forming a contact hole; filling the contact hole with aconductive plug on the at least one interlayer insulating layer; andforming the storage node according to claim
 20. 25. The method of claim24, wherein the at least one interlayer insulating layer includes afirst interlayer insulating layer.
 26. The method of claim 24, whereinforming the switching element includes forming a transistor type or adiode type.
 27. The method of claim 20, wherein the lower electrodelayer and the upper electrode layer are respectively composed ofthermoelectric materials having different conductivity types from eachother.
 28. The method of claim 21, wherein the lower electrode layer,the phase change layer, and the upper electrode layer are respectivelyformed of material layers having different seeback coefficients fromeach other.
 29. The method of claim 21, wherein when seebackcoefficients of the lower electrode layer, the phase change layer, andthe upper electrode layer are S1, S2 and S3 respectively, the lowerelectrode layer, the phase change layer, and the upper electrode layerare respectively formed of material layers such that S1, S2 and S3satisfy one relation of a relation of S1<S2<S3, a relation of S1<S3<S2,and a relation of S2<S1<S3.
 30. The method of claim 29, wherein in therelation of S1, S2 and S3, S1 and S3 satisfy a relation of S3−S1>100μV/K (K: absolute temperature).
 31. The method of claim 23, wherein thelower electrode layer is formed of an n-type thermoelectric materiallayer, and the upper electrode layer is formed of a p-typethermoelectric material layer, or the lower electrode layer is formed ofa p-type thermoelectric material layer, and the upper electrode layer isformed of an n-type thermoelectric material layer.
 32. The method ofclaim 20, wherein filling the via hole with a phase change layerincludes: forming a phase change material layer filling the via hole onthe second interlayer insulating layer; and polishing an upper surfaceof the phase change material layer until the second interlayerinsulating layer is exposed.
 33. The method of claim 32, afterpolishing, the method further comprising: lowering a height of an uppersurface of the second interlayer insulating layer than that of an uppersurface of the polished phase change material layer; and polishing theupper surface of the polished phase change material layer until thesecond interlayer insulating layer is exposed.